Ash-fall tuffs of the Pliocene-Pleistocene deposits of Humahuaca and Casa Grande intermountain basins, northwestern Argentina, have been differentiated into two groups based on new geochemical and geochronological data which correspond to the tuffs of the Pliocene-Lower Pleistocene alluvial fan deposits dominated by debris flow, deep sandy gravel braided, and shallow ephemeral lake deposits (Uquia and Mal Paso formations), and those recorded in Pleistocene alluvial fans sheet flood deposits. The two clusters of ages recognized: 4.3 to 2.6 Ma, and 2.2-pre 0.8 Ma, corresponding to these tuff groups, are in agreement with pulses of ignimbrite eruptions in the Altiplano Puna Volcanic Complex (APVC), and Southenn Puna calderas located west of the study region. The ash-fall tuffs of both groups are mainly vitreous to phenocryst-poor of rhyodacite-dacite composition with minor andesites to trachyandesites, characterized by 58-69% SiO2 contents, A/CNK 1-1.4, FeO/MgO (0.8-2.8), which plot in the calc-alkaline range. They can be differentiated based on its immobile trace elements ratios as indicated by a slight enrichment in LREE, higher arc affiliation and somewhat higher Sm/Yb ratios in the case of the younger group, although in both Sm/Yb ratios are indicative of sequestration of HREE in residual hornblende. The new geochemical and geochronological data of those ash fall tuffs point to these as chrono-stratigraphic tracers of the Humahuaca and Casa Grande intermountain basins stratigraphy, during the Pliocene-Pleistocene, also as the key to identify their volcanic sources.